Systems and methods to produce treated cellulose filaments and thermoplastic composite materials comprising treated cellulose filaments

ABSTRACT

A method and system to produce treated Cellulose Filaments (CF) and CF products are provided. Feedstock comprising CF in a water solution are mixed with a debonder to produce a mixed stream. The mixed stream is filtered yielding separate filtered and filtrate streams. The filtrate stream comprises at least a portion of the debonder. The filtered stream is dried to produce treated CF. The debonder is one of an alcohol, glycol ether, ester-containing quaternary ammonium salt, amido amine quaternary ammonium salt, disubstituted amide or a mixture thereof. The filtrate stream may be recycled. The mixed stream may be washed before filtering to remove debonder. A thermoplastic polymer-treated Cellulose filament composite material is formable by associating the treated CF with a thermopolymer such as polyolefin, polyurethane (PU), polypropylene (PP), polyester (PE), polylactic acid (PLA), polyhydroxyalcanoates (PHA), polyamide (PA), and ethylene vinyl acetate (EVA) or a mixture.

FIELD

The present matter relates to systems and methods to produce drydispersed Cellulose Filaments and thermoplastic composite materialscomprising dry dispersed Cellulose Filaments.

BACKGROUND

Cellulose Filaments are one type of cellulose fibre made in a mechanicalprocess in an aqueous suspension without the use of chemicals orenzymes. In this process, cellulose fibres (typically softwood kraftfibers) are split along their longest axis into over 1,000 CelluloseFilaments. The resulting Cellulose Filaments have similar fibre lengthand a high aspect ratio (e.g. a fibre length between 100 μm and 2,000 μmand a width between 30 nm and 500 nm). Typical solids levels for thefinished product aqueous suspension of Cellulose Filaments generallyrange from 25% to 45% (most commonly ˜30%).

Cellulose Filaments are very hydrophilic and can be easily dispersed inwater. Cellulose Filaments have a high density of —OH (hydroxyl) groupson their surface resulting in a strong tendency to form hydrogen bondswith each other. Uncontrolled drying of Cellulose Filaments leads tosolid Cellulose filaments “blocks” that are non-dispersible. However,due to their high surface area, strength characteristics, size andaspect ratio, Cellulose Filaments are an excellent candidate for makinglightweight composite materials.

Recently, the use of natural fibers such as cellulose as reinforcingagents in polymer composite materials has become of great interest.Natural cellulose-based fibers have the advantage of being low-cost,biodegradable, renewable, low density (compared to glass and othersynthetic fibers) and high specific stress and modulus.

However, natural fibers such as cellulose are generally not compatiblewith a hydrophobic polymer matrix. Rather, natural fibres such ascellulose tend to be hydrophilic and therefore form aggregates duringprocessing with hydrophobic polymer matrices. For example, due to thislack of compatibility with hydrophobic matrices, incorporation ofhydrophilic cellulose in thermoplastic composites leads to aggregationof cellulose therein. Further, natural fibres such as cellulosegenerally have high moisture/water absorption properties that limitpotential use in certain applications, such as in hydrophobic polymermatrices.

In the paper-making industry, high amounts of energy are typicallyrequired to fiberize pulp as pulp generally possesses strong inter-fiberhydrogen bonding. To reduce energy costs, efforts have been made toreduce hydrogen bonding among fibres in pulp lower the fiberizationenergy requirement during paper-making by adding organic and/orinorganic chemicals called debonders. Typically, debonders that havebeen used for this purpose are surfactants (e.g. substances that tendsto reduce the surface tension of a liquid in which it is dissolved).

Accordingly, there is a need for improved systems and methods for thedispersion of cellulose-based fibres such as Cellulose Filaments inthermoplastic matrices as a high dispersion of cellulose-based fibres inthermoplastic matrices is needed to obtain well-defined mechanicalproperties of resulting composite materials.

SUM MARY

A method and system to produce treated Cellulose Filaments (CF) and CFproducts are provided. Feedstock comprising CF in a water solution ismixed with a debonder to produce a mixed stream. The debonder is one ofan alcohol, glycol ether, ester-containing quaternary ammonium salt,amido amine quaternary ammonium salt, disubstituted amide or a mixturethereof. The mixed stream is filtered yielding separate filtered andfiltrate streams. The filtrate stream comprises at least a portion ofthe debonder and may be recycled. The filtered stream is dried toproduce treated CF. The mixed stream may be washed before filtering toremove debonder. A thermoplastic polymer-treated Cellulose filamentcomposite material is formable by associating the treated CF with athermopolymer such as polyolefin, polyurethane (PU), polypropylene (PP),polyester (PE), polylactic acid (PLA), polyhydroxyalcanoates (PHA),polyamide (PA), and ethylene vinyl acetate (EVA) or a mixture.

During the mixing stage the debonder may adsorb to a surface of theCellulose Filaments in a manner such that the debonder physically blocksthe hydroxyl groups on the surface of the Cellulose Filaments fromcontacting adjacent Cellulose Filaments, thereby weakening the effectsof hydrogen bonding between hydroxyl groups of adjacent CelluloseFilaments.

In one aspect, there is provided a method comprising: mixing a feedstockcomprising Cellulose Filaments in a water solution with a debonder toproduce a mixed stream; filtering the mixed stream to produce a filteredstream and a filtrate stream, the filtrate stream comprising at least aportion of the debonder; and drying the filtered stream to producetreated Cellulose Filaments; wherein the debonder is one of an alcohol,glycol ether, ester-containing quaternary ammonium salt, amido aminequaternary ammonium salt, disubstituted amide or a mixture thereof.

During mixing, the debonder adsorbs to a surface of the CelluloseFilaments in a manner such that the debonder physically blocks hydroxylgroups on the surface of the Cellulose Filaments from contactingadjacent Cellulose Filaments, thereby weakening the effects of hydrogenbonding between hydroxyl groups of adjacent Cellulose Filaments.

The Cellulose Filaments in the feedstock may comprise individual finethreads unraveled or peeled from natural cellulose fibers having afibrillar element width ranging from nanoscale (30 to 100 nm) tomicroscale (100 to 500 nm) and an aspect ratio of up to 5,000.

The feedstock may have a solids content of 30% Cellulose Filaments byweight.

The method may comprise, after mixing and before filtering, washing themixed stream with a washing alcohol or organic solvent to removeremaining debonder. In such a case, the debonder may comprise one of anester-containing quaternary ammonium salt, an amido amine quaternaryammonium salt and a disubstituted amide.

The method may further comprise recovering the debonder from thefiltrate stream and recycling the debonder to the mixing stage.

The method may comprise drying the filtered stream in two stages.

The method may further comprise associating the treated CelluloseFilaments and a thermoplastic polymer to produce a thermoplasticpolymer-treated Cellulose Filaments composite material.

The composite material may comprise 10 to 40% by weight treatedCellulose Filaments.

Associating may comprise mixing the treated Cellulose Filaments and thethermoplastic polymer to form a mixture and extruding the mixture.

The thermoplastic polymer may be one of a polyolefin, polyurethane (PU),polypropylene (PP), polyester (PE), polylactic acid (PLA),polyhydroxyalcanoates (PHA), polyamide (PA), and ethylene vinyl acetate(EVA) or a mixture. The polyolefin may comprise a polyethylene andwherein the polyethylene comprises low-density polyethylene (LDPE),linear low density polyethylene (LLDPE), maleated thermoplastic starch(mTPS) in LLDPE and high-density polyethylene (HDPE).

The thermoplastic polymer may be PA and the composite material comprise30% by weight treated Cellulose Filaments. The composite material mayhave a Young's Modulus gain of 181% compared to the thermoplasticpolymer alone. The composite material may have a tensile stress gain of73% compared to the thermoplastic polymer alone.

In one aspect, there is provided A system to produce treated CelluloseFilaments. The system comprises: a mixing stage for mixing a feedstockcomprising Cellulose Filaments in a water solution with a debonder toproduce a mixed stream; a filtering stage for filtering the mixed streamto produce a filtered stream and a filtrate stream, the filtrate streamcomprising at least a portion of the debonder; and a drying stage fordrying the filtered stream to produce the treated Cellulose Filaments.The debonder is one of an alcohol, glycol ether, ester-containingquaternary ammonium salt, amido amine quaternary ammonium salt,disubstituted amide or a mixture thereof.

During the mixing stage the debonder may adsorb to a surface of theCellulose Filaments in a manner such that the debonder physically blocksthe hydroxyl groups on the surface of the Cellulose Filaments fromcontacting adjacent Cellulose Filaments, thereby weakening the effectsof hydrogen bonding between hydroxyl groups of adjacent CelluloseFilaments.

The mixing stage may include a mixing vessel comprising a planetarymixer or a continuous high consistency pulp mixer.

The mixing stage and filtering stage may be combined such that themixing vessel is configured with a filter providing the filtering stage.

The filtering stage may comprise one of a Nutsche filter and a Buchnerfilter.

The drying stage may comprises one of a vacuum drying chamber,convention oven or Nutsche filter.

The system may be configured to add a washing alcohol or organic solventto the mixed stream to wash remaining debonder from the CelluloseFilaments of the mixed stream prior to filtering by the filtering stage.

The system may further comprise a recycling stage configured to recoverthe debonder and recycle the debonder to the mixing stage.

In an aspect there is provided a Cellulose Filaments product comprisingtreated Cellulose Filaments, the product produced in accordance with amethod aspect described herein. The method may comprise: mixing afeedstock comprising Cellulose Filaments in a water solution with adebonder to produce a mixed stream; filtering the mixed stream toproduce a filtered stream and a filtrate stream, the filtrate streamcomprising at least a portion of the debonder; and drying the filteredstream to produce the treated Cellulose Filaments. The debonder is oneof an alcohol, glycol ether, ester-containing quaternary ammonium salt,amido amine quaternary ammonium salt, disubstituted amide or a mixturethereof. The product may be a thermoplastic polymer-treated CelluloseFilaments composite material.

In one aspect there is provide a method to produce a thermoplasticpolymer-treated Cellulose Filaments composite material productcomprising: associating treated Cellulose Filaments with a thermopolymerto create a composite material; wherein the treated Cellulose Filamentscomprise Cellulose Filaments having individual fine threads unraveled orpeeled from natural cellulose fibers having a fibrillar element widthranging from nanoscale (30 to 100 nm) to microscale (100 to 500 nm) andan aspect ratio of up to 5,000 and that have been treated with adebonder comprising one of an alcohol, glycol ether, ester-containingquaternary ammonium salt, amido amine quaternary ammonium salt,disubstituted amide or a mixture thereof.

The composite material may comprise 10 to 40% by weight treatedCellulose Filaments. Associating may comprise mixing the treatedCellulose Filaments and the thermoplastic polymer to form a mixture andextruding the mixture.

The thermoplastic polymer may be one of a polyolefin, polyurethane (PU),polypropylene (PP), polyester (PE), polylactic acid (PLA),polyhydroxyalcanoates (PHA), polyamide (PA), and ethylene vinyl acetate(EVA) or a mixture. The polyolefin may comprise a polyethylene andwherein the polyethylene comprises low-density polyethylene (LDPE),linear low density polyethylene (LLDPE), maleated thermoplastic starch(mTPS) in LLDPE and high-density polyethylene (HDPE). The thermoplasticpolymer may be PA and the composite material comprise 30% by weighttreated Cellulose Filaments. The composite material may have a Young'sModulus gain of 181% compared to the thermoplastic polymer alone. Thecomposite material may have a tensile stress gain of 73% compared to thethermoplastic polymer alone.

BRIEF DESCRIPTION OF THE DRAWINGS

In order that the subject matter may be readily understood, embodimentsare illustrated by way of examples in the accompanying drawings, inwhich:

FIGS. 1A and 1B are block diagrams illustrating embodiments of a systemfor producing treated Cellulose Filaments;

FIG. 2 is a block diagram of a method for forming a thermoplasticpolymer-treated Cellulose Filaments composite.

FIG. 3 shows the differences in fluffiness of Cellulose Filamentssamples when treated with a debonder (e.g. Dowanol™ PnB);

FIG. 4 the differences in fluffiness of Cellulose Filaments samples whentreated with various debonders;

FIG. 5 shows the FT-IR spectra of Cellulose Filaments samples after twodifferent debonders treatments and the untreated Cellulose Filamentssample

FIG. 6 shows a graph depicting Young's modulus for three differentthermoplastic polymer-Cellulose Filaments composites prepared withvarying weight percentages of Cellulose Filaments;

FIG. 7 shows a graph depicting tensile stress for three differentthermoplastic polymer-Cellulose filaments composites prepared withvarying weight percentages of Cellulose Filaments;

FIG. 8 shows water absorption percentages over time for variouslow-density polyethylene (LDPE)-Cellulose filaments composites preparedwith varying weight percentages of Cellulose Filaments;

FIG. 9 shows water absorption percentages over time for varioushigh-density polyethylene (HDPE)-Cellulose filaments composites preparedwith varying weight percentages of Cellulose Filaments;

FIG. 10 shows water absorption percentages over time for variouspolypropylene (PP)-Cellulose filaments composites prepared with varyingweight percentages of Cellulose Filaments;

FIG. 11 shows water absorption percentages over time for variousLDPE-Cellulose Filaments composites, where the Cellulose Filaments weretreated with either propylene glycol n-butyl ether (Dowanol™ PnB) orSteposol® MET-10U/ethanol;

FIG. 12 shows a graph depicting Young's modulus for PA-CelluloseFilaments composites prepared with varying weight percentages ofCellulose Filaments; and

FIG. 13 shows a graph depicting tensile stress PA-Cellulose filamentscomposites prepared with varying weight percentages of CelluloseFilaments.

DETAILED DESCRIPTION

The description references various embodiments and examples unless it isexplicitly stated or it is logically incongruous otherwise, aspects orfeatures of any individual embodiment or example applies to the otherembodiments and examples. The term “cellulose” as used herein refers toa long-chain polymer polysaccharide carbohydrate comprised of β-glucosemonomer units, of formula (C₆H₁₀O₅)_(n), usually found in plant cellwalls in combination with lignin and any hemicelluloses, and therefore,the term cellulose also includes hemicelluloses. Sources of cellulosemay include any plant material containing cellulose, paper-products,waste streams containing cellulose, such as carbohydrate waste, etc.

The cellulosic structures referred to as Cellulose Filaments herein areproduced from natural cellulose fibers. Cellulose Filaments are neithercellulosic fibril bundles nor fibers branched with fibrils or separatedshort fibrils. Rather, Cellulose Filaments are individual fine threadsunraveled or peeled from natural cellulose fibers. Cellulose Filamentsare much longer than nanofibres, microfibrils, or nano-celluloses asdenoted in the prior art. Cellulose Filaments consist of a distributionof fibrillar elements of very high length (e.g. up to millimeters)compared to materials denoted microfibrillated cellulose, cellulosemicrofibrils, nanofibrils or nanocellulose. Their widths range from thenano size (e.g. 30 to 100 nm) to the micro size (100 to 500 nm). HereinCellulose Filaments comprise a width of about 30 to 300 nanometers and alength of at least 100 □m and up to 2 mm, thus possessing an extremelyhigh aspect ratio, typically of at least 200 and up to a few thousands.Because of their high aspect ratio, Cellulose Filaments form a gel-likenetwork in aqueous suspension at a very low consistency. The stabilityof the network can be determined by a settlement test described byWeibel and Paul (UK Patent Application GB 2296726), for example.

FIGS. 1A and 1B show embodiments of a system for producing dry dispersedCellulose Filaments according to some of the embodiments describedherein. Generally, system 100A and 100B comprises a mixing stage 102, afiltering stage 104 and a drying stage 106.

At mixing stage 102, a feedstock of Cellulose Filaments (e.g. insolution) 110 is mixed with a debonder 114 to form a mixed stream 116.

Filtering stage 104 follows mixing stage 102. At filtering stage 104,mixed stream 116 is filtered to form a filtered stream 122 and afiltrate 120.

Optionally, as shown in system 100A of FIG. 1A, after mixing stage 102and prior to filtering stage 104, a washing alcohol or organic solvent118 can be added to mixed stream 116 to wash the Cellulose Filamentstherein.

Drying stage 106 follows filtering stage 104. At drying stage 106,filtered stream 122 is dried to form a treated stream 124 comprising drydispersed Cellulose Filaments.

In some embodiments of system 100A and 110B, mixing stage 102, filteringstage 104 and the aforementioned optional washing of Cellulose Filamentsin mixed stream 116 with washing alcohol 118 can take place in a singlemixing vessel wherein feedstock 110 is mixed with debonder 114 and keptin suspension or solution (e.g. by stirring or agitation or shaking)while, optionally, washing alcohol 118 is added to form mixed stream116. Mixed stream 116 can subsequently be filtered (e.g. using a Buchnerfilter) to form filtered stream 122.

Mixing Stage 102

As shown in FIGS. 1A and 1B and according to one embodiment at mixingstage 102, a Cellulose filaments feedstock 110 is mixed with a debonder114 which may optionally include a first alcohol 112 as a debonder in amixing vessel. As described further below certain debonders may be mixedwith alcohol and in some embodiments, alcohol alone is used as adebonder. The width of the distribution of fibrillar elements comprisingthe Cellulose Filaments in feedstock 110 can range from nanoscale (e.g.30 to 100 nm) to microscale (e.g. 100 to 500 nm). The aspect ratio ofthe Cellulose Filaments used herein can be up to 5,000 and typically is400 to 1,000.

Cellulose Filament feedstock 110 may be 25%-45% solids, most commonlyCellulose Filaments feedstock 110 is 30% solids (by dry weight CelluloseFilaments). It is understood that a lower % below 25% is possible, butefficiency/economy may suffer.

Debonder 114 is added to feedstock 110 during mixing stage 102 toinhibit aggregation of Cellulose Filaments and promote dispersion ofCellulose Filaments when the Cellulose Filaments are put into use (e.g.as a strengthener in paper forming applications). In one embodiment,during mixing stage 102, debonder 114 adsorbs to a surface of theCellulose Filaments in a manner such that debonder 114 physically blocksthe hydroxyl groups on the surface of the Cellulose Filaments fromcontacting hydroxyl groups on the surface of adjacent CelluloseFilaments thereby weakening the effects of hydrogen bonding betweenhydroxyl groups of adjacent Cellulose Filaments. Weakening ofinter-filament hydrogen bonding and/or formation of a hydrophobic cloudsurrounding debonder-treated Cellulose Filaments can facilitateindividual Cellulose Filaments to be more readily dispersible insolution and can inhibit individual Cellulose Filaments from clustering,particularly after the mechanical mixing action of mixing stage 102ceases.

In one embodiment, debonder 114 can comprise any one of the followingclasses of debonders: alcohols, glycol ethers, ester-containingquaternary ammonium salts, amido amine quaternary ammonium salts,disubstituted amides, debonding mixtures. Combinations are also likelygiven the properties of the debonders.

In one embodiment, debonder 114 is an alcohol according to chemicalstructure (I) provided below, wherein R₁ is alkyl group.

R₁—OH   (I)

Examples of alcohols than can be used as debonder 114 include but arenot limited to methanol, ethanol, and butanol. Others such as propanoland isopropanol are expected to be effective as well. When debonder 114is an alcohol, first alcohol 112 may be unnecessary and not added.

In another embodiment, debonder 114 is glycol ether compound accordingto chemical structure (II) provided below.

In this embodiment, R₂ can be methyl, propyl or butyl groups and m canbe from 1 to 3. An example of a glycol ether compound that can be usedas debonder 114 includes but is not limited to Dowanol™ P-series glycolether supplied by the Dow Chemical Company.

In another embodiment, debonder 114 is an ester-containing quaternaryammonium salt or “ester quats” compound according to chemical structure(III) provided below.

In this embodiment, R₃ and R₄ can be the same or different and are C₁₋₆hydrocarbyl or hydroxyalkyl group, n can be from 1 to 6, preferably 1 to2. Each R₅ can be the same or different and is a linear or branchedC₅₋₃₅ alkyl or alkenyl chain preferably more than 11 atoms such astallow, and X can be an anion such as but not limited to chloride,bromide, methyl sulfate, ethyl sulfate, formate, acetate, carbonate,sulfate, nitrate and other like anions. In one preferred embodiment, Xis methyl sulfate. An example of an ester-containing quaternary ammoniumsalt that can be used as debonder 114 includes but is not limited toStepantex® VT-90 supplied by Stepan Company.

In another embodiment, debonder 114 is an amido amine quaternaryammonium salt compound according to chemical structure (IV) providedbelow.

In this embodiment, R₆ and R₇ can be the same or different are C₁₋₆ akylor hydroxyalkyl group, o can be from 1 to 6, preferably 1 to 2, p can be0 or 1, each R₈ can be the same or different and can be a linear orbranched alkyl or alkenyl chain comprising of at least 7 atoms andpreferably more than 11 atoms such as tallow, and X can be an anion suchas but not limited to chloride, bromide, methyl sulfate, ethyl sulfate,formate, acetate, carbonate, sulfate, nitrate and other like anions. Inone preferred embodiment, X is methyl sulfate. An example of an amidoamine quaternary ammonium salt that can be used as debonder 114 includesbut is not limited to Accosoft® 501 supplied by Stepan Company.

In another embodiment, debonder 114 can be a disubstituted amideaccording to chemical structure (V) provided below.

In this embodiment, R₉ can be a saturated or unsaturated alkyl chain andR₁₀ can be a saturated alkyl chain. An example of a disubstituted amidethat can be used as debonder 114 includes but is not limited toN,N-dimethyl 9-decenamide (e.g. Steposol® MET-10U supplied by StepanCompany).

In one embodiment, debonder 114 can be a mixture having two or morecomponents. In one embodiment, debonder 114 is a mixture comprising twocomponents, a first component being an alcohol according to chemicalstructure (I) noted above and a second component being a compoundaccording to any one of chemical structures (II) to (V) noted above(e.g. glycol ethers, an ester-containing quaternary ammonium salts,amido amine quaternary ammonium salts and disubstituted amides). Thefirst component and the second component of debonder 114 can be addedtogether or added separately to feedstock 110 at mixing stage 102.

In one embodiment, debonder 114 is polyethylene glycol butyl ether(PGBE).

In one embodiment, debonder 114 is mixed at mixing stage 102 withfeedstock 110 as feedstock 110 is constantly agitated and/or mixedwithin a mixing vessel. Debonder 114 can be mixed at mixing stage 102with feedstock 110 such that the resulting mixed stream 116 has a ratioof 2.5 grams of debonder 114 to 1 gram of dry Cellulose Filaments infeedstock 110.

In another embodiment, debonder 114 as a debonding mixture of alcohol(e.g. ethanol) and another debonder can be added to the mixing vessel ina range of ratios between 1:4 to 4:1. In one embodiment the ratio ofalcohol to other debonder is 1:1.

In one embodiment, the mixing vessel can be maintained at a temperaturewithin a range from 20° C. to 50° C. but below 30° C. is preferred.

In one embodiment, a retention time of feedstock 110 and debonder 114 inthe mixing vessel (e.g. Nutsche filter with recirculation) can varywithin a range of 15 min. to 24 hr and between 15 min. to 1 hr ispreferred.

While a suitable mixing vessel may include a Nutsche filter withrecirculation however any continuous high consistency pulp mixer may beutilized. If a planetary mixer with Nutsche filter is used, it can takebetween 30 min. and 2 hr at low shear. If a continuous pulp mixer isused, it may take only a few seconds at high shear.

In one specific embodiment, feedstock 110 can be added to the mixingvessel (with Nutsche filter) and debonder 114 as a mixture of PGBE andethanol can be subsequently added to the mixing vessel. The resultingsolution can be stirred for 1 hour while being maintained at about 20°C.

In one specific example, 333 grams of feedstock 110 (comprising 100grams of dry Cellulose Filaments) and debonder 114 as a mixturecomprising 130 mL of ethanol and 130 mL of PGBE can be mixed in a cakemixer for 1 hour at about 20° C.

In one specific example, 333 grams of feedstock 110 (comprising 100grams of dry Cellulose Filaments) and debonder 114 as a 1.72 L of PGBEcan be mixed in a cake mixer for 15 min at about 20° C.

Filtering Stage 104

Mixed stream 116 comprises Cellulose Filaments treated with debonder 114in solution. Mixed stream 116 may also comprise remaining debonder 114in solution. At filtering stage 104, the components of mixed stream 116are filtered into filtrate stream 120 and washed stream 122, whereCellulose Filaments treated with debonder 114 substantially comprisewashed stream 122. Nutsche or Buchner filters may be used for example.

In one embodiment, mixed stream 116 can optionally be washed with awashing alcohol or organic solvent 118 prior to filtering stage 104.Organic solvents such as acetone, dichloromethane or diethyl ether maybe used but alcohols as described above are preferred. During filteringstage 104, after debonder 114 has adsorbed to the surface of theCellulose Filaments in a manner that physically blocks the hydroxylgroups on the surface of the Cellulose Filaments from contactinghydroxyl groups on adjacent Cellulose Filaments, washing alcohol/organicsolvent 118 can be added to mixed stream 116 to remove remainingdebonder 114 from the Cellulose Filaments therein. When debonders ofchemical structures (III) to (V) are used they are typically washed.

In one embodiment, washing alcohol 118 can be added to mixed stream 116in a ratio from 6.7% to 9.4% CF (w/w) in ethanol: between 120 and 231 mlof ethanol for 20 g of dry CF.

In one example, 1.8 L of washing alcohol 118 can be added to mixedstream 116 prior to filtering stage 104 for each kilogram of dryCellulose Filaments in feedstock 110.

In one embodiment, mixed stream 116 can be filtered into filtrate stream120 and washed stream 122 using a Buchner filter.

It should be noted that any one or more of debonder 114 and washingalcohol 118 can be recovered in an optional recycling stage 108. Forexample, in one embodiment, at recycling stage 108, filtrate 120 canundergo further processing (not shown) to separate debonder 114 fromwashing alcohol 118 as well as to separate any one or more of the firstand second components of debonder 114 comprising a mixture for recyclingwithin system 100. In a further embodiment, at recycling stage 108,debonder 114 can be recovered by filtering debonder 114 from washingalcohol 118 as well as to filtering any one or more of the first andsecond components of debonder 114 comprising a mixture for recyclingwithin system 100. It should be noted that recycling stage 108 cancomprise separate filtering stages for separating debonder 114 fromwashing alcohol 118 and for separating individual components of debonder114 where debonder 114 is a mixture.

As noted above, not all debonders require washing. For example, whendebonders of chemical structure (II) were used, such as PGBE, withoutmixing with alcohol in the mixing stage 102 the PGBE can be recovered inthe optional recycling stage 108 (FIG. 1, 100B) without using a washingalcohol or solvent. In such a case the CF concentration was 5.7% (w/w).

Drying Stage 106

At drying stage 106, liquid content of washed stream 122 comprisingCellulose Filaments treated with debonder 114 is reduced to form treatedstream 124.

In one embodiment, drying stage 106 can remove excess moisture (e.g.water content and other liquid content such as alcohol and otherdebonders 114) from washed stream 122. Removing moisture from washedstream 122 can provide for the Cellulose Filaments treated with debonder114 to evenly disperse (e.g. inhibit aggregation) in subsequentapplications.

In one embodiment, Cellulose Filaments of washed stream 122 can be driedin a vacuum oven to evaporate excess moisture therein. Other dryingequipment may include a convection oven and Nutsche filter.

In one example, when 66.67 grams of feedstock 110 (30 wt % CelluloseFilaments in water) is mixed with 25 grams of debonder 114 (e.g. PGBE)and 25 grams of ethanol and subsequently washed with 120 mL of ethanoland filtered using a Buchner to form washed stream 122, washed stream122 can be dried in a vacuum oven in two stages: the first stagecomprising drying washed stream 122 at 70° C. for 2 hours and the secondstage comprising drying washed stream 122 at 120° C. for an additional 1hour.

Uses in Thermoplastic Composites

The present disclosure provides thermoplastic polymer-treated CelluloseFilaments composite materials and methods for forming thermoplasticpolymer-treated Cellulose filaments composite materials by associatingtreated Cellulose Filaments (e.g. treated with debonder 114 according toone of the embodiments described above) with a thermoplastic polymermatrix.

Herein, the term “composite” means a material which is composed of twoor more materials having different physical characteristics and in whicheach material retains some of its identity while contributing desirableproperties to the whole. For example, a thermoplastic polymer associatedwith treated Cellulose Filaments forms a thermoplastic polymer-treatedCellulose Filaments composite material, wherein each of thethermoplastic polymer and the treated Cellulose Filaments contributes tothe mechanical properties of the composite as a whole.

Herein, “associate” means to bring into relation with one another, as ifby mixing or blending. For example, a thermoplastic polymer can beassociated with treated Cellulose Filaments by mixing a resin of thethermoplastic polymer with treated Cellulose Filaments and then forming(e.g. extruding) the mixture into a polymer.

Thermoplastic polymers for inclusion in the thermoplasticpolymer-treated Cellulose Filaments composites described herein caninclude but are not limited to polyolefins such as polyethylenes (e.g.low-density polyethylene (LDPE), linear low density polyethylene(LLDPE), maleated thermoplastic starch (mTPS) in LLDPE and high-densitypolyethylene (HDPE)), polyurethane (PU), polypropylene (PP) (e.g.recycled), polyester (PE), polylactic acid (PLA), polyhydroxyalcanoates(PHA), polyamide (PA), and ethylene vinyl acetate (EVA).

In some embodiments, the composite materials described herein are about30% or less by weight of the composite treated Cellulose Filaments.

In one embodiment, the thermoplastic polymer-treated Cellulose filamentcomposite can be formed such that the composite comprises LDPE as thethermoplastic polymer in the composite. In another embodiment, thethermoplastic-treated Cellulose filament composite can be formed suchthat the composite comprises 50% or more by weight LDPE, preferably 60%or more by weight LDPE.

In another embodiment, the thermoplastic polymer-treated Cellulosefilament composite can be formed such that the composite comprises LDPEas the thermoplastic polymer in the composite and the composite has aYoung's Modulus greater than the Young's Modulus of LDPE. In oneembodiment, the thermoplastic polymer-treated Cellulose filamentcomposite can be formed such that the composite comprises LDPE as thethermoplastic polymer and the composite has a Young's Modulus gain of109%.

In another embodiment, the thermoplastic polymer-treated Cellulosefilament composite can be formed such that the composite comprises LDPEas the thermoplastic polymer in the composite and the composite has atensile stress greater than the tensile stress of LDPE. In oneembodiment, the thermoplastic polymer-treated Cellulose filamentcomposite can be formed such that the composite comprises LDPE as thethermoplastic polymer and the composite has a tensile stress gain of 63%

In another embodiment, the thermoplastic polymer-treated Cellulosefilament composite can be formed such that the composite comprises LDPEas the thermoplastic polymer in the composite and the composite has atotal elongation at break less than the total elongation at break ofLDPE. In one embodiment, the thermoplastic polymer-treated Cellulosefilament composite can be formed such that the composite comprises LDPEas the thermoplastic polymer and the composite has an elongation atbreak of 10%.

In another embodiment, the thermoplastic polymer-treated Cellulosefilament composite can be formed such that the composite comprises LDPEas the thermoplastic polymer in the composite and the composite hasgreater water absorption than LDPE. In one embodiment, the thermoplasticpolymer-treated Cellulose filament composite can be formed such that thecomposite comprises LDPE as the thermoplastic polymer and the compositehas a water absorption of 3.5-4.0% after 96 hours.

In another embodiment, the thermoplastic polymer-treated Cellulosefilament composite can be formed such that the composite comprises HDPEas the thermoplastic polymer in the composite. In one embodiment, thethermoplastic polymer-treated Cellulose filament composite can be formedsuch that the composite comprises 50% or more by weight HDPE, preferably60% or more by weight HDPE.

In another embodiment, the thermoplastic polymer-treated Cellulosefilament composite can be formed such that the composite comprises HDPEas the thermoplastic polymer in the composite and the composite has aYoung's Modulus greater than the Young's Modulus of HDPE. In oneembodiment, the thermoplastic polymer-treated Cellulose filamentcomposite can be formed such that the composite comprises HDPE as thethermoplastic polymer and the composite has a Young's Modulus gain of63%.

In another embodiment, the thermoplastic polymer-treated Cellulosefilament composite can be formed such that the composite comprises HDPEas the thermoplastic polymer in the composite and the composite has atensile stress greater than the tensile stress of HDPE. In oneembodiment, the thermoplastic polymer-treated Cellulose filamentcomposite can be formed such that the composite comprises HDPE as thethermoplastic polymer and the composite has a tensile stress gain of39%.

In another embodiment, the thermoplastic polymer-treated Cellulosefilament composite can be formed such that the composite comprises HDPEas the thermoplastic polymer in the composite and the composite has atotal elongation at break less than the total elongation at break ofHDPE. In one embodiment, the thermoplastic polymer-treated Cellulosefilament composite can be formed such that the composite comprises HDPEas the thermoplastic polymer and the composite has an elongation atbreak of about 12%.

In another embodiment, the thermoplastic polymer-treated Cellulosefilament composite can be formed such that the composite comprises HDPEas the thermoplastic polymer in the composite and the composite hasgreater water absorption than HDPE. In one embodiment, the thermoplasticpolymer-treated Cellulose filament composite can be formed such that thecomposite comprises HDPE as the thermoplastic polymer and the compositehas a water absorption of about 7% after one year.

In another embodiment, the thermoplastic polymer-treated Cellulosefilament composite can be formed such that the composite comprises PP asthe thermoplastic polymer in the composite. In one embodiment, thethermoplastic polymer-treated Cellulose filament composite can be formedsuch that the composite comprises 50% or more by weight PP, preferably60% or more by weight PP.

In another embodiment, the thermoplastic polymer-treated Cellulosefilament composite can be formed such that the composite comprises PP asthe thermoplastic polymer in the composite and the composite has aYoung's Modulus greater than the Young's Modulus of PP. In oneembodiment, the thermoplastic polymer-treated Cellulose filamentcomposite can be formed such that the composite comprises PP as thethermoplastic polymer and the composite has a Young's Modulus gain of32%.

In another embodiment, the thermoplastic polymer-treated Cellulosefilament composite can be formed such that the composite comprises PP asthe thermoplastic polymer in the composite and the composite has atensile stress greater than the tensile stress of PP. In one embodiment,thermoplastic polymer-treated Cellulose filament composite can be formedsuch that the composite comprises PP as the thermoplastic polymer andthe composite has a tensile stress gain of 30%.

In another embodiment, the thermoplastic polymer-treated Cellulosefilament composite can be formed such that the composite comprises PP asthe thermoplastic polymer in the composite and the composite has a totalelongation at break less than the total elongation at break of PP. Inone embodiment, the thermoplastic polymer-treated Cellulose filamentcomposite can be formed such that the composite comprises PP as thethermoplastic polymer and the composite has an elongation at break ofabout 6%.

In another embodiment, the thermoplastic polymer-treated Cellulosefilament composite can be formed such that the composite comprises PP asthe thermoplastic polymer in the composite and the composite has greaterwater absorption than PP. In one embodiment, the thermoplasticpolymer-treated Cellulose filament composite can be formed such that thecomposite comprises PP as the thermoplastic polymer and the compositehas a water absorption of about 3.6% after 96 hours.

It is understood that blends of polymers, such as PP and PE, asdescribed in other references regarding thermoplastics may be usedherein. The compositions contemplated herein can additionally compriseconventional additives used in formation of thermoplastic polymersincluding plasticizers, stabilizers including viscosity stabilizers andhydrolytic stabilizers, antioxidants, ultraviolet ray absorbers,anti-static agents, dyes, pigments or other coloring agents, inorganicfillers, fire-retardants, lubricants, reinforcing agents such as glassfiber and flakes, foaming or blowing agents, processing aids, antiblockagents, release agents, and/or mixtures thereof. Optional additives,when used, can be present in various quantities so long as they are notused in an amount that detracts from the basic characteristics of thecomposition.

The composite composition can be produced by any methods known to oneskilled in the art such as combining any type of cellulose material(e.g. treated Cellulose Filaments) with a thermoplastic polymer (e.g. aribbon blender or any low intensity mixer commonly used in blendingsolids). The mixture can be processed in a heated extruder attemperatures suitable for processing the particular thermoplasticpolymer chosen.

FIG. 2 shows an exemplary method 200 for forming a thermoplasticpolymer-treated Cellulose filament composite. Method 200 comprises step202 of inserting a thermoplastic (e.g. PE, PP, etc. as described)polymer (e.g. resin) into an extruder and meting the thermoplasticpolymer. At step 204, additional thermoplastic polymer and treatedCellulose Filaments are added to the extruder and mixed. At step 206,the mixed thermoplastic polymer and treated Cellulose Filaments arefurther mixed to obtain homogeneous samples. The resulting homogenouscomposite material is removed from the rolls of the extruder and can becut into strips according to the size of the mold.

Step 202 comprises inserting a thermoplastic resin into the extruder andmeting the resin. In one embodiment, the thermoplastic resin is meltedon the rollers of the extruder at 170° C. (e.g. when the thermoplasticpolymer is LDPE and HDPE) or 180° C. (e.g. when the thermoplasticpolymer is PP).

At step 204, additional thermoplastic polymer and treated CelluloseFilaments are added to the extruder and mixed. In one embodiment,additional thermoplastic polymer and treated Cellulose Filaments areadded to the extruder and mixed at 50 rpm for 7 minutes. In anotherembodiment, after the additional thermoplastic polymer and treatedCellulose Filaments are added to the extruder and mixed at 50 rpm for 7minutes, the composite material can be further mixed for 15 minutes toobtain homogeneous samples.

In one specific example, 80 grams of thermoplastic (e.g. LDPE, HDPE orPP) and 20 grams of Cellulose Filaments are added to the extruder andmixed at 50 rpm for 7 minutes.

At step 206, the resulting composites can be removed from the rolls andcut into strips according to the size of the mold. The compositematerial can be formed into shaped articles using methods such asinjection molding, compression molding, overmolding, or extrusion.Optionally, formed articles comprising the composite materials describedherein can be further processed. For example, pellets, slugs, rods,ropes, sheets and molded articles of the compositions described hereinmay be prepared and used for feedstock for subsequent operations, suchas thermoforming operations, in which the article is subjected to heat,pressure and/or other mechanical forces to produce shaped articles.Compression molding is an example of further processing.

The composite material can be cut, injection molded, compression molded,overmolded, laminated, extruded, milled or the like to provide thedesired shape and size to produce commercially usable products. Examplesof resultant products include: packaging, container, automotive industry(engine cover, cam cover, battery tray, door panel) etc.

The following examples are set forth to aid in the understanding of thedescription provided and should not be construed to limit in any way thescope of the claims which follow hereafter.

EXAMPLES Evaluation of the Fluffiness of Treated Cellulose Filaments

The fluffiness of Cellulose Filaments gives a good appreciation of thefuture dispersion of Cellulose Filaments (e.g. dispersion within athermoplastic polymer matrix). As is shown in FIG. 3, visual inspectionof Cellulose Filaments with or without treatment provides that varyingdegrees of fluffiness are provided upon treatment of Cellulose Filamentswith a debonder (e.g. propylene glycol n-butyl ether (PGBE) such asDowanol™ PnB). Specifically, FIG. 3 shows fluffiness of samples ofCellulose Filaments (10 grams) with and without treatment (as indicatedthereon).

“Fluffiness” herein refers to the Cellulose Filaments being ‘light’ or‘airy’ such that Cellulose Filaments of equal mass with a higherfluffiness tend to resist settling under gravity more than CelluloseFilaments with lower fluffiness. Fluffiness can be measured as aquantity (e.g. weight) per unit volume.

As shown in FIG. 3, Cellulose Filaments treated with a debonder showedmore fluffiness than Cellulose Filaments that were not treated with adebonder.

Efficiency of debonder treatment was further evaluated by visuallymeasuring “fluffiness” of treated Cellulose Filaments. FIG. 4 shows acomparison of fluffiness of 10 grams of Cellulose Filaments that weretreated with various debonders. For example, as depicted on FIG. 4,treatment with a Dowanol™ PnB/methanol mixture increased the fluffinessof Cellulose Filaments when compared to treatment with an Accosoft®501/ethanol mixture.

Treatment of Cellulose Filaments with Debonders

In the examples below, the following debonders were used:

TABLE 1 Characteristics for the debonders used in the examples belowDebonder MW Boiling point Flash point Propylene glycol n-butyl ether 132171° C.  63° C. (Dowanol ™ PnB) Ethanol 46  78° C. 16.60° C.  N,N-dimethyl 9-decenamide 197 297° C. 134° C. (Steposol ® MET-10U)

Example 1 Treatment of Cellulose Filaments with a Mixture ofPGBE/Ethanol (in a 1:1 Weight Ratio) and Incorporation of the TreatedCellulose Filaments in LDPE, HDPE and PP

In one example, 66.67 grams of wet Cellulose Filaments (30% CelluloseFilaments w/w in water) and a solution of PGBE (Dowanol™ PnB)/ethanol ina 1:1 ratio by weight (25 grams of PGBE and 25 grams of ethanol) weremixed into a cake mixer during 1 hour at room temperature. 120 mL ofethanol was added to the Cellulose Filaments as a washing alcohol anddebonder mixture and the resulting mixture was filtrated using a Buchnerfilter. The product from the filter was dried in a vacuum oven in twostages: first at 70° C. for 2 hours and then at 120° C. for 1 hour. Thedried Cellulose Filaments were finely pulverized and the resultingfluffy treated Cellulose Filaments were subsequently associated withLDPE, HDPE and PP according to the method provided below.

Association of Treated Cellulose Filaments with Thermoplastic Polymers

In the examples below, the following thermoplastics were used (Table 2):

TABLE 2 Characteristics for the thermoplastic polymer matrices used inthe examples below Young's % modulus Tensile stress Elongation atThermoplastic matrix (MPa) (MPa) break Low-density polyethylene 216 ± 3419.5 ± 1.1 >500% (LDPE) High-density polyethylene 487 ± 25 37.7 ±1.8 >100% (HDPE) Polypropylene (PP) 541 ± 36   27 ± 1.3

Cellulose Filaments treated with debonders were associated with LDPE,HDPE and PP according to the following examples.

In one example, thermoplastic polymer-treated Cellulose filamentcomposites were manufactured in two stages using a two-roller extruder(C.W Brabender® with Thermotron model T-303; C.W Brabender® Instruments,Inc. South Hackensack, N.J., USA). In the first stage, 80 grams ofthermoplastic (LDPE, HDPE or PP) were melted on the rollers of theextruder at 170° C. (LDPE and HDPE) or 180° C. (PP). In the secondstage, 20 grams of treated Cellulose Filaments were added and mixed at50 rpm for 7 minutes. The composites were further mixed for 15 minutesto obtain homogeneous samples. The resulting composites were removedfrom the rolls and cut into strips according to the size of the mold.

The composites were molded into dumb-bell shapes (e.g. ASTM D638-type V)for mechanical property testing. A total of 10 tensile samples wereprepared at 170±3° C. for 10 minutes, in a single mold of a Dake brandpress (from Dake Division of JSJ Corporation) at 15 MPa. The mold wascooled by cold water circulation until 60° C.

The same procedure was used to prepare composite made with 10%, 30% and40% w/w of treated Cellulose Filaments.

Mechanical Properties Studies

Composites formed as described above were conditioned overnight in atesting room at 23° C. and 50% relative humidity, polished and measuredwith a micrometer prior to testing. The mechanical measurements wereperformed on an Instron tester (model 4201; Norwood, Mass., USA). Eachspecimen had an approximate width of 0.28-0.30 cm and an approximatethickness of 0.32-0.34 cm. A minimum of five samples were tested in eachseries. The mechanical properties obtained for each series of compositesare depicted below.

FIG. 6 shows a graph depicting Young's Modulus for three differentthermoplastic polymer-treated Cellulose filament composites preparedwith varying weight percentages of Cellulose Filaments.

FIG. 7 shows a graph depicting tensile stress for three differentthermoplastic polymer-treated Cellulose filament composites preparedwith varying weight percentages of Cellulose Filaments.

As shown in FIG. 7, the tensile properties of thermoplastics are largelyimproved (e.g. increased Young's Modulus and increased tensile stress)by adding treated Cellulose Filaments to each thermoplastic polymermatrix as treated Cellulose Filaments generally have higher stress andstiffness values than those of the thermoplastic polymer.

Association of treated Cellulose Filaments in thermoplastic polymers asdescribed resulted in a significant decrease of the total elongation atbreak (see Table 3). This may be attributable to the lower elongationvalues of treated Cellulose Filaments when compared to eachthermoplastic polymer used. Such a modification of elongation suggests atransition from a ductile behavior corresponding to a thermoplasticcomposite to a rather brittle character.

TABLE 3 Elongation at break (%) for different thermoplasticpolymer-treated Cellulose filament composites Low-density High-densitypolyethylene (LDPE) polyethylene (HDPE) Polypropylene (PP) % Wt of 0 1020 30 40 0 10 20 30 40 0 10 20 30 40 Cellulose Filaments Total >500 3817 15 10 >100 15 12 13 12 15 13 9 8 6 elongation at break (%)

Water Absorption of Thermoplastic-Treated Cellulose Filament Composites

Rectangular samples were cut from each thermoplastic polymer-treatedCellulose filament composite with dimension size of approximately 21mm×9.5 mm×2.9 mm. These samples were soaked in distilled water andremoved at different times, wiped with filter paper and dried withcompressed air. The samples were weighed regularly at 20, 48, 72 and 96hours, 1 month and 6 months exposure with an analytical balance with 0.1mg resolution. Water absorption was calculated according to thefollowing formula:

Increase in weight (%)=[(Wet weight−Initial weight)/Initial weight]×100

FIGS. 8 to 10 show water absorption for treated Cellulose Filamentscomposites with LDPE, HDPE and PP, respectively.

The results indicate that the water absorption characteristics of thethermoplastic polymers were modified by the addition treated CelluloseFilaments. This may be due to the great affinity to water of the treatedCellulose Filaments. Generally, water absorption of the compositesincreased with increased weight percentages of treated CelluloseFilaments to the thermoplastic resin. The evolution of water absorptionover time is described for the LDPE-treated Cellulose filamentcomposites at different weight percentages of treated CelluloseFilaments (FIG. 8), HDPE-treated Cellulose filament composites atdifferent weight percentages of treated Cellulose Filaments (FIG. 9) andPP-treated Cellulose filament composites at different weight percentagesof treated Cellulose Filaments (FIG. 10). An increase in waterabsorption over the water absorption of each polymer matrix alone isnoted with the addition of treated Cellulose Filaments in eachcomposite.

Example 2 Treatment of Cellulose Filaments with PGBE and Incorporationof the Treated Cellulose Filaments in LDPE

In one example, 66.67 grams of wet Cellulose Filaments (30% CelluloseFilaments w/w in water) and 304 grams of PGBE (Dowanol™ PnB) were mixedinto a cake mixer during 15 minutes at room temperature. The resultingmixture was filtrated using a Buchner filter. The product from thefilter was dried in a vacuum oven in two stages: first at 70° C. for 2hours and then at 120° C. for 1 hour. The dried Cellulose Filaments werefinely pulverized and the resulting fluffy treated Cellulose Filamentswere associated with LDPE to form composite materials.

Incorporation of Treated Cellulose Filaments into Thermoplastic Matrices

The procedure described above in Example 1 was used to prepare thedifferent thermoplastic polymer matrices.

Mechanical Properties Studies

The procedure described above in Example 1 was used to study themechanical properties of thermoplastic polymer-treated Cellulosefilament composites where the treated Cellulose Filaments were treatedwith PGBE (Dowanol™ PnB). The mechanical properties obtained for acomposite prepared with 20% of treated Cellulose Filaments and 80% ofLDPE are described in Table 4.

TABLE 4 Mechanical properties for a composite 20% treated CelluloseFilaments - 80% polyethylene Young's Tensile % modulus stress Elongation(MPa) (MPa) at break 386 ± 11 31 ± 1.2 15%

Example 3 Treatment of Cellulose Filaments with a Mixture ofN,N-dimethyl 9-decenamide (Steposol® MET-10U)/Ethanol in a Ratio of 1:4by Weight and Incorporation of the Treated Cellulose Filaments in LDPE

66.67 g of wet Cellulose Filaments (30% Cellulose Filaments w/w inwater) and a solution of N,N-dimethyl 9-decenamide (Steposol®MET-10U)/ethanol in a 1:4 ratio by weight (e.g. 10 grams of Steposol®MET-10U and 40 grams of ethanol) were mixed into a cake mixer during 1hour at room temperature. 2×200 mL of ethanol was added and the mixtureof Cellulose Filaments and debonder and the resulting mixture wasfiltrated using a Buchner filter. The resulting mixture was dried in avacuum oven in two stages: first at 70° C. for 2 hours and then at 120°C. for 1 hour. The dried Cellulose Filaments were finely pulverized andthe resulting fluffy treated Cellulose Filaments were then used to formcomposite materials with LDPE.

Incorporation of Treated Cellulose Filaments into Thermoplastic Matrices

The procedure described above in Example 1 was used to prepare thedifferent thermoplastic polymer matrices.

Mechanical Properties Studies

The procedure described above in Example 1 was used to study themechanical properties of thermoplastic polymer-treated Cellulosefilament composites where the treated Cellulose Filaments were treatedwith Steposol® MET-10U/ethanol in a 1:4 ratio as a debonder. Themechanical properties obtained for a composite prepared with 20% oftreated Cellulose Filaments and 80% of LDPE are described in Table 5.

TABLE 5 Mechanical properties for a composite 20% treated CelluloseFilaments - 80% polyethylene Young's Tensile % modulus stress Elongation(MPa) (MPa) at break 323 ± 9 25.3 ± 1.1 19%

Water Absorption of Cellulose Filament Composites

The procedure described above in Example 1 was used to study waterabsorption of thermoplastic polymer-treated Cellulose filamentcomposites where the treated Cellulose Filaments were treated withSteposol® MET-10U/ethanol in a 1:4 ratio by weight. The waterabsorptions observed for the thermoplastic polymer-treated Cellulosefilament composites treated respectively with PGBE ((Dowanol™ PnB) andN,N-dimethyl 9-decenamide (Steposol® MET-10U)/ethanol are depicted inFIG. 11.

Treatment of Cellulose Filaments with different debonders (e.g. Dowano™PnB and Steposol® MET-10U/ethanol) does not appear to significantlyalter the water absorption of the resulting composites.

FIG. 12 shows a graph depicting Young's modulus for PA-CelluloseFilaments composites prepared with varying weight percentages ofCellulose Filaments; and FIG. 13 shows a graph depicting tensile stressPA-Cellulose filaments composites prepared with varying weightpercentages of Cellulose Filaments.

What is claimed is:
 1. A method comprising: mixing a feedstockcomprising Cellulose Filaments in a water solution with a debonder toproduce a mixed stream; filtering the mixed stream to produce a filteredstream and a filtrate stream, the filtrate stream comprising at least aportion of the debonder; and drying the filtered stream to producetreated Cellulose Filaments; wherein the debonder is one of an alcohol,glycol ether, ester-containing quaternary ammonium salt, amido aminequaternary ammonium salt, disubstituted amide or a mixture thereof. 2.The method of claim 1, wherein during mixing, the debonder adsorbs to asurface of the Cellulose Filaments in a manner such that the debonderphysically blocks hydroxyl groups on the surface of the CelluloseFilaments from contacting adjacent Cellulose Filaments, therebyweakening the effects of hydrogen bonding between hydroxyl groups ofadjacent Cellulose Filaments.
 3. The method of claim 1 wherein theCellulose Filaments in the feedstock comprise individual fine threadsunraveled or peeled from natural cellulose fibers having a fibrillarelement width ranging from nanoscale (30 to 100 nm) to microscale (100to 500 nm) and an aspect ratio of up to 5,000.
 4. The method of claim 1,wherein the feedstock has a solids content of 30% Cellulose Filaments byweight.
 5. The method of claim 1 comprising, after mixing and beforefiltering, washing the mixed stream with a washing alcohol or organicsolvent to remove remaining debonder.
 6. The method of claim 5 whereinthe debonder comprises one of an ester-containing quaternary ammoniumsalt, an amido amine quaternary ammonium salt and a disubstituted amide.7. The method of claim 1 further comprising recovering the debonder fromthe filtrate stream and recycling the debonder to the mixing stage. 8.The method of claim 1 comprising drying the filtered stream in twostages.
 9. The method of claim 1, further comprising associating thetreated Cellulose Filaments and a thermoplastic polymer to produce athermoplastic polymer-treated Cellulose Filaments composite material.10. The method of claim 9 wherein the composite material comprises 10 to40% by weight treated Cellulose Filaments.
 11. The method of claim 9wherein associating comprises mixing the treated Cellulose Filaments andthe thermoplastic polymer to form a mixture and extruding the mixture.12. The method of claim 9 wherein the thermoplastic polymer is one of apolyolefin, polyurethane (PU), polypropylene (PP), polyester (PE),polylactic acid (PLA), polyhydroxyalcanoates (PHA), polyamide (PA), andethylene vinyl acetate (EVA) or a mixture.
 13. The method of claim 11wherein the polyolefin comprises a polyethylene and wherein thepolyethylene comprises low-density polyethylene (LDPE), linear lowdensity polyethylene (LLDPE), maleated thermoplastic starch (mTPS) inLLDPE and high-density polyethylene (HDPE).
 14. The method of claim 11wherein the thermoplastic polymer is PA and the composite materialcomprises 30% by weight treated Cellulose Filaments.
 15. The method ofclaim 11 wherein the composite material has a Young's Modulus gain of181% compared to the thermoplastic polymer alone.
 16. The method ofclaim 11 wherein the composite material has a tensile stress gain of 73%compared to the thermoplastic polymer alone.
 17. A system to producetreated Cellulose Filaments, the system comprising: a mixing stage formixing a feedstock comprising Cellulose Filaments in a water solutionwith a debonder to produce a mixed stream; a filtering stage forfiltering the mixed stream to produce a filtered stream and a filtratestream, the filtrate stream comprising at least a portion of thedebonder; and a drying stage for drying the filtered stream to producethe treated Cellulose Filaments; wherein the debonder is one of analcohol, glycol ether, ester-containing quaternary ammonium salt, amidoamine quaternary ammonium salt, disubstituted amide or a mixturethereof.
 18. The system of claim 17, wherein during the mixing stage thedebonder adsorbs to a surface of the Cellulose Filaments in a mannersuch that the debonder physically blocks the hydroxyl groups on thesurface of the Cellulose Filaments from contacting adjacent CelluloseFilaments, thereby weakening the effects of hydrogen bonding betweenhydroxyl groups of adjacent Cellulose Filaments.
 19. The system of claim17, wherein the mixing stage includes a mixing vessel comprising aplanetary mixer or a continuous high consistency pulp mixer.
 20. Thesystem of claim 17, wherein the mixing stage and filtering stage arecombined such that the mixing vessel is configured with a filterproviding the filtering stage.
 21. The system of claim 17, wherein thefiltering stage comprises one of a Nutsche filter and a Buchner filter.22. The system of claim 17, wherein the drying stage comprises one of avacuum drying chamber, convention oven or Nutsche filter.
 23. The systemof claim 17 configured to add a washing alcohol or organic solvent tothe mixed stream to wash remaining debonder from the Cellulose Filamentsof the mixed stream prior to filtering by the filtering stage.
 24. Thesystem of claim 17 further comprising a recycling stage configured torecover the debonder and recycle the debonder to the mixing stage.
 25. ACellulose Filaments product comprising treated Cellulose Filaments, theproduct produced in accordance with a method comprising: mixing afeedstock comprising Cellulose Filaments in a water solution with adebonder to produce a mixed stream; filtering the mixed stream toproduce a filtered stream and a filtrate stream, the filtrate streamcomprising at least a portion of the debonder; and drying the filteredstream to produce the treated Cellulose Filaments; wherein the debonderis one of an alcohol, glycol ether, ester-containing quaternary ammoniumsalt, amido amine quaternary ammonium salt, disubstituted amide or amixture thereof.
 26. The Cellulose Filaments product of claim 25 whereinthe product is a thermoplastic polymer-treated Cellulose Filamentscomposite material.
 27. A method to produce a thermoplasticpolymer-treated Cellulose Filaments composite material productcomprising: associating treated Cellulose Filaments with a thermopolymerto create a composite material; wherein the treated Cellulose Filamentscomprise Cellulose Filaments having individual fine threads unraveled orpeeled from natural cellulose fibers having a fibrillar element widthranging from nanoscale (30 to 100 nm) to microscale (100 to 500 nm) andan aspect ratio of up to 5,000 and that have been treated with adebonder comprising one of an alcohol, glycol ether, ester-containingquaternary ammonium salt, amido amine quaternary ammonium salt,disubstituted amide or a mixture thereof.
 28. The method of claim 27wherein the composite material comprises 10 to 40% by weight treatedCellulose Filaments.
 29. The method of claim 27 wherein associatingcomprises mixing the treated Cellulose Filaments and the thermoplasticpolymer to form a mixture and extruding the mixture.
 30. The method ofclaim 28 wherein the thermoplastic polymer is one of a polyolefin,polyurethane (PU), polypropylene (PP), polyester (PE), polylactic acid(PLA), polyhydroxyalcanoates (PHA), polyamide (PA), and ethylene vinylacetate (EVA) or a mixture.
 31. The method of claim 30 wherein thepolyolefin comprises a polyethylene and wherein the polyethylenecomprises low-density polyethylene (LDPE), linear low densitypolyethylene (LLDPE), maleated thermoplastic starch (mTPS) in LLDPE andhigh-density polyethylene (HDPE).
 32. The method of claim 30, whereinthe thermoplastic polymer is PA and the composite material comprises 30%by weight treated Cellulose Filaments.
 33. The method of claim 30,wherein the composite material has a Young's Modulus gain of 181%compared to the thermoplastic polymer alone.
 34. The method of claim 30,wherein the composite material has a tensile stress gain of 73% comparedto the thermoplastic polymer alone.